Method of making a catalyst

ABSTRACT

A method of making a catalyst. The method comprises the step of leaching alloy particles. Preferably, the alloy particles are hydrogen storage alloy particles.

RELATED APPLICATION INFORMATION

This application is a divisional application of application Ser. No.09/523,820 filed on Mar. 13, 2000, U.S. Pat. No. 6,841,512, which is acontinuation-in-part of application Ser. No. 09/290,633 filed on Apr.12, 1999, U.S. Pat. No. 6,270,719. application Ser. No. 09/523,820, U.S.Pat. No. 6,841,512 is hereby incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to catalysts and more specifically tomethods of making catalysts.

BACKGROUND OF THE INVENTION

A fuel cell is an electrochemical device in which the chemical energy ofa conventional fuel is converted directly and efficiently into lowvoltage electrical energy. Fuel cells have many potential applicationssuch as supplying power for transportation vehicles, replacing steamturbines and remote power supply applications.

Fuel cells, like conventional batteries, operate by utilizingelectrochemical reactions. Unlike a battery, in which chemical energy isstored within the cell, fuel cells generally are supplied with reactantsfrom outside the cell. Barring failure of the electrodes, as long as thefuel (preferably hydrogen), and the oxidant (preferably either oxygen orair that contains oxygen) are supplied and the reaction products areremoved, the cell continues to operate.

Fuel cells also offer a number of important advantages over engine orgenerator systems. They include relatively highly efficient,environmentally clean operation especially when utilizing hydrogen as afuel, high reliability, few moving parts, and quiet operation.

A schematic diagram of a fuel cell with the reactant/product gases andthe ion conduction flow directions through the cell is shown in FIG. 4.Referring to FIG. 4, the major components of a typical fuel cell 10 isan anode 14, a cathode 16 and an electrolyte layer 12. In the embodimentshown, the anode 14 and the cathode 16 are each in contact with andpositioned on opposite sides of the electrolyte layer. During operation,a continuous flow of fuel, commonly hydrogen, is fed to the anode 14while, simultaneously, a continuous flow of oxidant, commonly oxygen orair, is fed to the cathode 16. In the example shown, the hydrogen is fedto the anode 14 via a hydrogen compartment 13. Likewise, the oxygen orair is fed to the cathode 16 via an oxygen/air compartment 17. The fuelis oxidized at the anode with a release of electrons through the agencyof a catalyst. These electrons are conducted from the anode 14 throughwires external to the cell, through the load 18, to the cathode 16 wherethe oxidant is reduced and the electrons are consumed, again through theagency of a catalyst. The constant flow of electrons from the anode 14to the cathode 16 constitutes an electrical current that can be made todo useful work. Typically, the reactants such as hydrogen and oxygen,are respectively fed through the porous anode 14 and cathode 16 andbrought into surface contact with the electrolyte 12. The particularmaterials utilized for the anode 14 and cathode 16 are important sincethey must act as efficient catalysts for the reactions to take place.

Despite their potential advantages, fuel cells have not been widelyutilized due in large part to their relatively high cost. An importantfactor contributing to this high cost is the catalytic inefficiencies ofthe prior art catalytic materials and/or the high costs of many of thesematerials. The catalytic inefficiencies of the materials increase theoperating costs of the fuel cell since such inefficiencies result in alower electrical energy output for a given amount of fuel. The use ofexpensive catalytic materials, such as noble metal catalysts, results infuel cells which are too expensive for widespread application.

High catalytic efficiency at low cost is a desired result which must beattained before widespread commercial utilization of fuel cells ispossible. Prior art fuel cell anode catalysts, which have been generallypredicated on either expensive noble metal catalysts with a relativelylow density of catalytically active sites, have not been able to meetthe requirements. The present invention is directed toward novel, lowcost and highly efficient catalytic materials that are useful for avariety of applications such as a fuel cell anode. The present inventionis also directed toward an efficient and inexpensive method of makingthe novel catalytic materials.

SUMMARY OF THE INVENTION

An objective of the present invention is an inexpensive, highlycatalytic material that may be used for facilitating hydrogenconsumption in a fuel cell anode. Another objective of the presentinvention is a catalytic material having a finely divided metalparticulate with very small particle size. Yet another objective of thepresent invention is a cost effect method for making the instantcatalytic materials. Yet another objective of the present invention is afuel cell anode and a fuel cell incorporating the instant catalyticmaterials.

These and other objectives are satisfied by a catalyst lacking platinumand palladium, the catalyst comprising: a metal particulate having aparticle size less than about 100 Angstroms; and a support.

These and other objectives are also satisfied by a catalyst, comprising:a nickel and/or nickel alloy particulate having a particle size lessthan about 100 Angstroms, the nickel alloy lacking platinum andpalladium; and a support.

These and other objectives are also satisfied by a catalyst comprising ametal particulate and a support, the catalyst characterized by beingformed by the process comprising the step of leaching at least asignificant portion of the bulk of a hydrogen storage alloy.

These and other objectives are satisfied by a method for making acatalyst, comprising the steps of: providing a hydrogen storage alloy;and leaching at least a significant portion of the bulk of the alloy.

These and other objectives are satisfied by a fuel cell, comprising: ananode having a catalyst lacking platinum and palladium, the catalystcomprising: a metal particulate having a particle size less then about100 Angstroms, and a support. The fuel cell preferably further comprisea cathode and an electrolyte. The electrolyte may comprise an alkalinematerial.

These and other objectives are satisfied by a fuel cell, comprising: ananode having a catalyst comprising: a nickel and/or nickel alloyparticulate having a particle size less than about 100 Angstroms, thenickel alloy lacking platinum and palladium, and a support. The fuelcell preferably further comprises a cathode and an electrolyte. Theelectrolyte may comprise an alkaline material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an STEM photomicrograph showing the effects of leaching ahydrogen storage alloy particle with an alkaline solution;

FIG. 2 is an STEM photomicrograph of the instant catalytic material,performed under Brightfield imaging, showing the catalytically activenickel rich regions;

FIG. 3 is an STEM photomicrograph, performed under Darkfield imaging, ofthe same region of catalytic material from FIG. 2;

FIG. 4 is a schematic diagram of a fuel cell;

FIG. 5 is a diagram of an alkaline fuel cell using the catalyst of thepresent invention;

FIG. 6 is a diagram showing an example of an anode layer for an alkalinefuel cell comprising a catalyst and a hydrophobic material;

FIG. 7 is a diagram showing cell voltage and pressure versus time for aNi-MH cell charged at C/10 rate for twenty hours;

FIG. 8 is a diagram showing cell voltage and pressure versus time forthe Ni-MH cell of FIG. 7, with the cell kept idle in the openconfiguration for five hours;

FIG. 9 is a diagram showing cell voltage and pressure versus time for aNi-MH cell charged and discharge after multicycling and then charged atC/10 rate for twenty hours; and

FIG. 10 is a diagram showing cell voltage and pressure versus time forthe Ni-MH cell of FIG. 9, with the cell kept in open circuit in the openconfiguration for five hours.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein is a novel catalyst particularly useful forfacilitating the consumption of molecular hydrogen in a fuel cell anode.The catalyst is designed to have a high density of catalytically activesites to provide efficient, low cost fuel cell operation. With a greaterdensity of catalytically active sites, the hydrogen oxidation reactionoccurs much more readily to allow for more efficient hydrogenconsumption at reduced costs.

Generally, the catalyst of the present invention comprises a metalparticulate, and a support. The particulate may be affixed to thesurface of the support. Alternately, the particulate may be partially ortotally embedded into the support. The metal particulate is a pluralityof metal particles. Preferably, each metal particle may be asubstantially pure elemental metal, or it may be an alloy of two or moreelemental metals. It is also possible that one or more of the individualparticles may be a composite or mixture of two or more elemental metals,two or more alloys, or an elemental metal and an alloy. All of theparticles may have the same composition or they may be a mixture ofparticles with different compositions. Also, some of the particles maybe substantially pure elemental metals while others may be alloys of twoor more elemental metals.

In one preferred embodiment of the present invention, the catalyst lacksboth platinum and palladium. Hence, there are no platinum particles orpalladium particles. As well, none of the metal particles compriseeither platinum or palladium as part of an alloy, composite or mixture.

In another embodiment of the present invention, the metal particulatecomprises nickel particles and/or nickel alloy particles. The nickelalloy includes nickel and at least one additional elemental metal.Preferably, the at least one additional elemental metal may be anyelemental metal except for either platinum or palladium. (Hence, it ispreferable that the nickel alloy lacks both platinum and palladium).More preferably, the at least one additional elemental metal is selectedfrom the group consisting of Al, Co, Sn, Mn, Ti and Fe. Most preferably,the at least one additional elemental metal is selected from the groupconsisting of Al, Co, Sn, Mn, and Ti. Examples of nickel alloys whichmay be used include nickel alloys comprising Ni and Co; nickel alloyscomprising Ni, Co and Al; nickel alloys comprising Ni, Co, Mn and Ti;nickel alloys comprising Ni, Co, Mn and Fe; and nickel alloys comprisingNi and Mn. Specific examples of nickel alloys include a NiCo alloy, aNiCoAl alloy, a NiCoMnTi alloy, a NiCoMnFe alloy, and a NiMn alloy.

It is believed that the addition of modifier elements to the nickel toform a nickel alloy increases the surface roughness of the metalparticles. Since surface roughness is the total surface area divided bythe geometric surface area, the increased roughness provides for anincrease in the total surface area of the metal particulate. Theincreased surface area provides for an increase in the number of activecatalysis sites (i.e., there is increased accessibility to the catalyticmaterial). Hence, the catalytic activity of the material is increased.

The increased surface area also makes the catalytic material less easyto poison. This is a crucial factor in the commercial viability of fuelcell anodes. Generally, poisoning is reduced as the number of activecatalysis sites increases. As just discussed, this occurs with increasedsurface roughness and surface area. (It is noted that surface area canalso be increased in other ways besides increasing surface roughness.For example, surface area may be increased by making the metal catalyticparticles smaller and packing them closer together. This will alsodecrease the chance of the poisoning).

The addition of modifier elements to the metallic nickel can alsoinhibit poisoning in other ways. Poisoning can be affected by the actualcomposition of the metallic particulate. By identifying the poison andthe mechanism for poisoning, a suitable modifier may be added to themetal particulate to combat the poisoning. For example, poisoning may bedue to the build-up of a passivating oxide on the surface of the metalparticulate, thereby impeding the H₂ dissociation reaction. In thiscase, a modifier element such as cobalt or aluminum could be added at aconcentration which is effective to provide an ongoing leaching of theparticulate by the electrolyte in order to constantly provide a clean,new metallic surface which is free of the passivating oxide.

Also, poisoning may be due to the corrosion of the particulate and/orits support by the electrolyte. In this case a passivating agent, suchas Zr or Mn, could be added. Though not wishing to be bound by theory,it is possible that these modified catalysts may be especially resistantto H₂ contaminants such as H₂S, CH₄, CO₂, CO, which are aggressivepoisons to fuel cell anode catalysts.

It is also believed that adding certain elements, such as Al, Sn and Co,to the nickel to form the nickel alloy may actually inhibit the growthof the alloy particles and cause the average size of the particles toremain small. As discussed above, decreasing the particle size whilepacking the particles closer together increases the total surface areaof the particulate, increasing catalytic activity and decreasing thepossibility of poisoning.

The catalytic metal particles of the present invention are not limitedto any particular shape. They may be regularly shaped or irregularlyshaped. Examples of particle shapes include spherical, elongated,thread-like, and “sponge-like”. “Sponge-like”, porous particles may bemade by initially including in the metal particulate a modifier element,such as aluminum, whose sole purpose is to be leached out so as to leavethe catalyst particulate with a sponge-like shape and a high surfacearea. The leaching step may be carried out by subjecting the alloy to anaqueous solution of an alkali metal hydroxide such as potassiumhydroxide, lithium hydroxide, sodium hydroxide, or mixtures thereof.Preferably, the leaching may be done in a highly concentrated KOHsolution (perhaps about 45 wt % to about 60 wt %), at elevatedtemperature of about 80° C. to about 120° C., for a time of about onehour to about four hours. Of course, other leaching conditions are alsopossible. After the leaching step, the remaining insoluble componentforms a particulate with a sponge-like, porous structure. The increasedporosity increases the surface area of the particulate.

It is noted that the catalytic activity of a material may be determinedby measuring the materials exchange current I_(o) (measured in mA/g).The exchange current I_(o) is a function of both the material's exchangecurrent density i_(o) (measured in mA/m²) as well as the material'ssurface area A (m²/g). Specifically, the exchange current, the exchangecurrent density and the surface area are all related as follows:I _(o) =i _(o) ×A  (1)

Equation (1) shows that the total catalytic activity of a material (asmeasured by the total exchange current I_(o)) is a function of both thecatalytic activity of the material composition (as measured by theexchange current density i_(o)) as well as the surface area of thematerial A. Hence, the total catalytic activity of a material may beincreased by either appropriately changing its composition to one whichis more catalytic or by increasing its effective surface area. Asdiscussed above, the effective surface area may be increased byincreasing the porosity and/or roughness of the catalytic particles. Italso may be increased by using a larger number of smaller-sizedparticles, and by packing these smaller-sized particles closer together.The effective surface area may also be increased by increasing theporosity and surface area of the support upon which active material isdispersed. The support will be discussed in more detail below.

Preferably, the catalytic metal particles of the present invention havea very small particle size. Specifically, the particles have an averageparticle size which is preferably less than about 100 Angstroms, morepreferably less than about 70 Angstroms, and most preferably less thanabout 50 Angstroms. In addition, the particles may have an averageparticle size which is preferably be less than about 40 Angstroms andmore preferably may have an average particle size which is less thanabout 30 Angstroms. In addition, the particulate may have a particlesize between about 10 to about 70 Angstroms, preferably between about 10to about 50 Angstroms, more preferably between about 10 to about 40Angstroms and most preferably between about 10 and about 30 Angstroms.

A key aspect of the instant invention is the disclosure of a practicalembodiment and method of producing “ultra fine catalysts”. Since thecatalytic properties of a material are primarily a surface property(rather than a bulk property), large catalytic metal particlesessentially waste the interior metallic atoms. For expensive elements,such as platinum and palladium (well known to have the requiredstability for fuel cell anode use), this waste of material provides anunacceptable cost. Therefore, the smaller the metallic particles, thebetter since the surface area for catalysis rises proportionally. It isextremely difficult to produce Angstrom size metallic particles. Hence,the disclosure of 10–50 Angstrom size particles (which themselves mayhave additional surface area due to surface roughness) in a finelydivided distribution within an inexpensive support is unique.

In certain embodiments of the present invention, the metal particles ofthe present invention are situated in close proximity to one another sothat the particulate has a high density. (Hence, there is also a highdensity of catalytic activity). The particulate may have an averageproximity that is preferably between about 2 and about 300 Angstroms,and more preferably between about 50 to about 100 Angstroms.

In other embodiments of the invention the percentage weight of the metalmay be varied so that the metal particulate is preferably between about0.0001% to about 99% by weight of the catalyst, more preferably betweenabout 0.001% to about 99% by weight of the catalyst, most preferablybetween about 0.01% to about 99% by weight of the catalyst.

Experimental observations from high resolution scanning transmissionelectron microscopy (STEM) of specific embodiments of the instantcatalytic material show the presence of catalytic regions or “catalyticclouds”. These catalytic regions may comprise nickel and/or nickel alloyregions. The nickel or nickel alloy regions may be regions of metallicnickel particles and/or nickel alloy particles having an average size ofabout 10 to about 30 Angstroms in diameter. In some of these regions,the proximity between the particles may be between about 10 to about 50Angstroms. In other regions, the metallic nickel and/or nickel alloyparticles are even more closely packed, having a proximity on the orderof about 10 to about 20 Angstroms. Specifically, FIG. 2 is an STEMphotomicrograph of the instant catalytic material, performed underBrightfield imaging, showing the catalytically active nickel richregions. FIG. 3 is an STEM photomicrograph, performed under Darkfieldimaging, of the same region of catalytic material from FIG. 2. FIG. 3shows the metallic nickel particles.

Preferably, the metal particulate of the present invention is “stable”over time. That is, preferably, the size of the particles remains smalland does not increase over time. This helps to ensure that the totalsurface area of the particulate remains stable (i.e., does not decrease)over time.

The catalyst of the present invention further comprises a support forthe metal particulate. Generally, any support conventionally known inthe art, capable of supporting and providing adequate dispersion for theparticulate, may be used. Preferably, the support should be inexpensiveand stable in the local environment in which it is being used. Thesupport used preferably has a surface area and/or porosity sufficient toprovide an adequate dispersion of the metal particles, thereby allowingboth penetration of electrolyte for the anode reaction, but preferablynot allowing the electrolyte to penetrate to the H₂ gas compartment.

Increasing the porosity of the support also provides for a more intimatecontact between the hydrogen gas reactant and the catalytic material. Inthe case of a liquid electrolyte, it also enhances the contact betweenthe electrolyte and the catalytic particles thereby improving oroptimizing proton transfer. Generally, the metal particulate may beaffixed to the surface of a support and/or partially embedded in thesupport and/or totally imbedded in the support.

The instant invention also facilitates introduction of an electrolyteimpermeable membrane in combination with a current collection substratesuch as wire mesh or expanded metal.

In one embodiment of the present invention, the support comprises one ormore inorganic oxides. The inorganic oxides may be metal oxides. Theoxides may comprise at least one element selected from the groupconsisting of nickel, cobalt, manganese, titanium, zirconium, iron andthe rare earth elements. The oxides may comprise one or more individualoxides of the elements nickel, cobalt, manganese, titanium, zirconium,iron and the rare earth elements. Alternately, the oxides may compriseone or more oxides of alloys formed from two or more of the elementsnickel, cobalt, manganese, titanium, zirconium, iron and the rare earthelements.

In a first example, the support comprises an oxide of manganese. In asecond example, the support comprises an oxide of nickel and manganese.In a third example, the support comprises an oxide of nickel, manganese,cobalt, and titanium. In a fourth example, the support comprises anoxide of nickel, manganese, cobalt, titanium and iron. In a fifthexample, the support comprises an oxide of nickel, manganese, cobalt andtitanium. In a sixth example, the support comprises an oxide of titaniumand zirconium. In a seventh example the support comprises silica. In aneighth example, the support comprises alumina. The metal particulate maybe affixed to the surface of the oxide support. Alternately, the metalparticulate may be at least partially embedded within the oxide support,or it may be totally embedded within the oxide support.

In still another preferred embodiment of the instant invention, theseultra-fine catalysts may be combined with zeolite materials. Thezeolites may have variable metal to silicon ratios, and the ratio of thecatalyst to zeolite may also vary. A combination of catalyst/supportoxide/zeolite is a preferred embodiment.

The oxide support may itself be catalytic. In fact, by using certainoxides as the support material, regions of exceptionally high catalyticactivity may be formed, especially at the double or triple or morejunctions between the metallic particle and the support oxide wheredesigned regions of hydrophobic or hydrophilic property may be formed.Analytical studies show that these regions are rich in such elements asnickel, cobalt, manganese and titanium, and are referred to herein as“NiCoMnTi super catalytic regions”. It is believed that these supercatalytic regions may consist of nickel-manganese alloy particlesembedded in a titanium-zirconium oxide. These super catalytic regionsshow a surprising lack of oxygen (based on the results of ElectronEnergy Loss Spectroscopy-EELS). It is also believed that the oxideportion of these regions may be partially metallic and/or exist in a lowoxidation state.

The oxide support also may be formed from metal oxides which are“microcrystalline” in structure, having crystallites of very small size.Because of their small crystallite size, these oxides have an increasednumber of grain boundaries which provide “ionic pathways” for bothhydrogen and hydroxyl ions. (These ionic pathways may permit thehydrogen and hydroxyl ions to more more freely to the metallic nickel ornickel alloy catalytic sites which may be situated in the grainboundaries). Hence, such oxides facilitate ionic transport through thecatalytic material.

Alternately, the oxide support may be formed so that it at leastpartially comprises a “multivalent” oxide material such as manganeseoxide, MnO_(x). Because manganese oxide is multivalent, it is believedthat it may further promote increased catalytic activity by changingoxidation states.

It is also possible to add a polymeric material to the oxide support inorder to modify the hydrophobic/hydrophilic nature of the catalyst bed.Examples of such polymers include fluropolymers such aspolytetrafluoroethylene (PTFE).

The oxide support may comprise fine-grained oxides, coarse-grainedoxides or a mixture of fine-grained oxides and coarse-grained oxides.Alternately, the oxide support may be formed so that it comprises a“multi-phase” oxide material. For example, the oxide may be formed sothat it includes both fine-grained and coarse-grained regions. Thefine-grained region may include oxides such as a manganese oxideMnO_(x), a NiMnCoTi oxide or a MnCoTi oxide. One advantage of amultiphase oxide may be the suitable structural integrity of the fuelcell anode to withstand the rigors of transportation where vibration cancause premature fuel cell failure. The coarse-grained regions mayinclude oxides such as a TiZr oxide.

The catalytic materials of the present invention may be formed so thatthe metal particles have certain crystal structures (based on SelectArea Electron Diffraction—SAED) within the oxide support. For example,catalytic materials comprising nickel alloy particles embedded within anoxide material may be formed so that the alloy particles have aface-center-cubic (fcc) structure. The formation of an fcc crystalstructure may be influenced by the high degree of substitution of themodifier elements (such as Co, Al, Mn, Sn) for the nickel. The fccnickel alloy in conjunction with the NiCoMnTi super catalytic regionsand the TiZr oxide forms a structure which may further promote ionicdiffusion and reaction. In an alternate embodiment of the presentinvention, the support may be formed from a carbon material. Examples ofcarbon supports include carbon black, graphite, activated carbon,charcoal and carbine. Mixtures of carbon materials and inorganic oxidesmay also be used. Alternately, the support may comprise a carbide. Forexample, the support may comprise a binary compound of carbon andanother element. (Examples of carbides include those of calcium,tungsten, silicon, boron, and iron). Additionally, other mixtures orblends of supports can be used to provide high surface area for thecatalytic metal particulate and good electronic conductivity as well asgood ionic transport.

Alternately, the support may comprise a halide such as a chloride.Alternately, the support may comprise a phosphide, a silicide, or anitride. Of course, the support may be a blend or mixture of thematerials described above.

One of the starting materials for the formation of the catalyticmaterials of the present invention are hydrogen storage alloys. Theseare materials which are capable of the absorption and release ofhydrogen. Hydrogen storage alloys are known in the art. Examples of verysimple hydrogen storage alloys are the TiNi and LaNi₅ alloys. Otherexamples of hydrogen storage alloys are provided in U.S. Pat. No.4,623,597 (the disclosure of which is incorporated by reference). Thematerials described in the '597 patent have a greatly increased densityof catalytically active sites providing for the fast and stable storageand release of hydrogen. These materials were fabricated by manipulatingthe local chemical and structural order by incorporating selectedmodifier elements into a host matrix so as to create the desireddisorder. Additional hydrogen storage alloys are disclosed in U.S. Pat.No. 4,551,400 (“the '400 patent”), the disclosure of which isincorporated by reference. These materials utilize a generic Ti—V—Nicomposition where at least Ti, V, and Ni are present with at least oneor more of Cr, Zr, and Al. Other Ti—V—Zr—Ni alloys are described in U.S.Pat. No. 4,728,586 (“the '586 patent”), the disclosure of which isincorporated by reference. The '586 patent described a specificsub-class of these Ti—V—Ni—Zr alloys comprising Ti, V, Zr, Ni, and afifth component Cr. Modified LaNi₅ materials are discussed in U.S. Pat.No. 5,096,667, (“the '667 patent”) the contents of which is incorporatedby reference herein. Still other examples of hydrogen storage alloys aredescribed in U.S. Pat. Nos. 5,840,440, 5,536,591 (“the '591 patent”) andin commonly assigned U.S. Patent application Ser. No. 09/290,633 (“the'633 application”). The contents of U.S. Pat. Nos. 5,840,440, and5,536,591 as well as the contents of U.S. patent application Ser. No.09/290,633 are all incorporated by reference herein.

Examples of alloys described in the '591 patent are alloys having thecomposition:(Base Alloy)_(a)Co_(b)Mn_(c)Fe_(d)Sn_(e)where Base Alloy comprises 0.1 to 60 atomic percent Ti, 0.1 to 40 atomicpercent Zr, 0 to 60 atomic percent V, 0.1 to 57 atomic percent Ni, and 0to 56 atomic percent Cr; b is 0 to 7.5 atomic percent; c is 13 to 7atomic percent; d is 0 to 3.5 atomic percent; e is 0 to 1.5 atomicpercent; and a+b+c+d+e=100 atomic percent. Many of the alloys describedin the '591 patent include Mn, the effects of which is discussed in the'667 patent, the disclosure of which is incorporated by referenceherein.

The '633 application describes certain hydrogen absorbing alloys formedby adding one or more modifier elements to certain “base” alloys. Thebase alloys preferably have a composition consisting essentially of 0.1to 60% Ti, 0.1 to 40% Zr, 0 to 60% V, 0.1 to 57% Ni, 5 to 22% Mn and 0to 56% Cr. The modified alloys which are described in the '633application are referred to herein as “the '633 alloys”.

Preferably, the modifying elements are chosen from the group consistingof Al, Co, Sn, and Fe. More preferably, the modifying elements arechosen from the group consisting of Al, Co, and Sn. In a first example,all three modifying elements, Al, Co, and Sn are added to the basealloy. In a second example, all four modifying elements, Al, Co, Sn andFe are added to the base alloy. In a third example, the modifierelements may added to the base alloy so that the atomic percentage of Alis between about 0.1 and about 10, the atomic percentage of the Co isbetween about 0.1 and about 10, the atomic percentage of the Sn isbetween about 0.1 and about 3.0, and the atomic percentage of the Fe isbetween about 0.0 and about 3.5. In a fourth example, the modifierelements may be added to the base alloy so that the resulting modifiedalloy has the following composition:Ti_(9.0)Zr_(26.2)V_(5.0)Vi_(38.0)Cr_(3.5)Co_(1.5)Mn_(15.6)Al_(0.4)Sn_(0.8).

Hydrogen storage alloys tend to react with oxygen to form metal oxidesby the reaction:M+x/2O₂->MO_(x)  (2)Hydrogen storage alloys are sensitive to the formation of surface oxidesso that most, if not all, of these alloys comprise an initial surfaceoxide layer. The composition of this initial surface oxide layerdepends, at least in part, on the composition of the underlying bulkalloy material (that is, upon the constituent metals which make up thebulk material as well as the atomic percentage of those metals). Theoxide surface layer is typically between about 50 Angstroms to about1000 Angstroms thick, although thicknesses of the surface oxide layer ofup to about 5000 Angstroms are possible.

The initial surface oxide of a hydrogen storage alloy may be modified byan etch process. Alkaline etch processes are described in U.S. Pat. No.4,716,088 (“the '088 patent”) as well as in commonly assigned U.S.patent application Ser. No. 09/395,391 (“the '391 application”). Boththe '088 patent as well as the '391 application are incorporated byreference herein. As described in the '088 patent, the major role of theetch process is that of surface modification. The '088 patent, '391application as well as the '591 patent and the '633 application describethe effects of the etch process on the surface oxide.

A method of making the catalytic material of the present invention is bysubjecting a hydrogen storage alloy starting material (which ispreferably in the form of a powder) to a leaching process (also referredto herein as a “leaching treatment”). The leaching process of thepresent invention is a deep, penetrating “bulk” leaching process. Thismeans that the leaching material (the active material that does theleaching—also referred to as “leaching agent” or “leachant”) penetrateswell below the 5000 Angstrom initial surface oxide layer of the alloyparticle and into the particle bulk. As used herein, “bulk” refers tothe interior region of the particle beneath the 5000 Angstrom oxidesurface layer. The leaching process penetrates and treats (i.e.,leaches) at least a significant portion of the bulk of the alloyparticle. Preferably, a significant portion of the bulk is leached whenthe leaching process treats at least about 10,000 Angstroms of thehydrogen storage alloy particle. Hence, it is preferable that at leastabout a 10,000 Angstrom thick layer of the hydrogen storage alloyparticle is leached. More preferably, at least about 20,000 Angstroms ofthe particle is leached. Most preferably, at least about 30,000Angstroms of the particle is leached. In another embodiment of themethod, it is preferable to leach at least about 40,000 Angstroms of theparticle. It is more preferable to leach at least about 50,000 Angstromsof the particle. In a preferred embodiment of the method, it ispreferable to leach substantially the entire bulk of the hydrogenstorage alloy material. Hence, in a preferred embodiment, substantiallythe entire hydrogen storage alloy particle is leached.

In other embodiments of the instant invention preferably at least about10% of the hydrogen storage alloy particle is leached, more preferablyat least about 25% of the hydrogen storage alloy particle is leached,and most preferably at least about 50% of the hydrogen storage alloyparticle is leached. In yet other embodiment of the instant inventionpreferably at least about 75% of the hydrogen storage alloy particle isleached, and more preferably at least about 90% of the hydrogen storagealloy particle is leached.

As described above, an embodiment of the instant catalytic materials isa finely divided metal particulate embedded in an oxide support. Inparticular, the metal particulate may be a metallic nickel and/or anickel alloy where the nickel alloy lacks both platinum and palladium.This embodiment may be made by subjecting the hydrogen storage alloymaterial to the appropriate leaching process. The leaching processpenetrates into substantially the entire particle bulk and converts theoxidizable components of substantially the entire bulk of the alloyparticle to oxides. Hence, the oxidizable components of substantiallythe entire alloy particle in converted to oxides.

The hydrogen storage alloy may be subjected to a leaching process by“contacting” the alloy material with an appropriate leaching materialfor a predetermined period of time, at a specific temperature and at aspecific pH. To convert the alloy material to oxide, the appropriateleaching material may be an alkaline solution. The hydrogen storagealloy may be “contacted” with the alkaline solution by placing the alloy(which is preferably in powder form) in a container of the alkalinesolution. The alkaline solution is preferably formed as an aqueoussolution of an alkali metal hydroxide. Examples of alkali metalhydroxides which may be used include potassium hydroxide, sodiumhydroxide, lithium hydroxide, and mixtures thereof. The pH of thealkaline solution may be adjusted by changing its alkalineconcentration. The alkaline concentration is adjusted by changing thepercentage weight of the alkali metal hydroxide added to the aqueoussolution. The period of time in which the leaching material (i.e, inthis case, the alkaline solution) is in contact with the hydrogenstorage alloy, as well as the temperature and pH of the leaching agentare all result-effective variables which can be varied to effect theoutcome of the leaching process.

Many of the metallic components within the bulk of the alloy are readilyoxidized by the concentrated alkaline solution of the leaching process.However, some of the metallic elements and/or alloys within the bulk ofthe alloy are resistant to oxidation by the alkaline solution. Bychoosing an appropriate starting alloy and then subjecting this startingalloy to the alkaline solution for a certain period of time and at acertain temperature and pH, it is possible to convert the oxidizablecomponents to oxides. However, some of the metallic components and/oralloy components are resistance to oxidation by the alkaline solutionand are not converted oxides. In fact, by carefully selecting theappropriate starting hydrogen storage alloy as well as the appropriateleaching conditions, the starting alloy may be leached so thatsubstantially all of the oxidizable components of the hydrogen storagealloy material are converted to oxides. Those components which areresistant to oxidation will remain as metallic elements or alloys.

Hence, in a preferred embodiment of the catalytic material of thepresent invention may be formed by selecting an appropriate startinghydrogen storage alloy material and then leaching the material with theappropriate leaching material and under the appropriate conditions(i.e., time, temperature and pH) until substantially all of theoxidizable components of the starting hydrogen storage alloy areconverted to oxides (i.e., so that substantially none of the oxidizablecomponents of the hydrogen storage alloy remain). This “completelyoxidized” material includes a finely divided, highly catalytic metaland/or alloy particulate (which is preferably nickel and/or nickelalloy) that, as discussed above, is resistant to conversion to oxide bythe alkaline solution. The oxidized material with metal particulate maybe referred to herein as a “catalytic oxide”. The metal particulate maybe extremely small. As discussed the particles may be made which have anaverage particle size which is preferably less than about 100 Angstroms,more preferably less than about 70 Angstroms, and most preferably lessthan about 50 Angstroms. In addition, in certain embodiments of thepresent invention the particulate may have a particle size between about10 to about 70 Angstroms, preferably between about 10 to about 50Angstroms, more preferably between about 10 to about 40 Angstroms, mostpreferably between about 10 to about 30 Angstroms.

Hence, the leaching process provides a cost effective way to make acatalytic material comprising metallic nickel and/or nickel alloyparticles having an extremely small particle size (i.e., ultra-finemetallic catalysts). It is noted that if one wished to make the samesize nickel or nickel alloy particles using metallurgical means it wouldeither not be possible, or if possible, would be cost prohibitive. Inparticular, it is noted that background art U.S. Pat. No. 4,541,905 toKuwana, et al. (“the '905 patent”) describes a catalytic material formedby the electrodeposition of nickel into a polymeric layer. In contrastto the instant catalytic materials, the catalytic material of the '905patent comprises nickel oxide rather than elemental metallic nickel.Likewise background art U.S. Pat. No. 5,053,379 to Giordano, et al.(“the '379 patent”) also describes a nickel catalyst made by subjectinga nickel compound carrier to a thermal decomposition treatment. Incontrast to the present invention, the Ni/MgO catalyst of the '379patent also consists of nickel oxide rather than metallic nickel.

In addition to converting essentially all of the oxidizable componentsof the hydrogen storage alloy material to oxides, the leaching treatmentmay also alter the composition of the oxides. The alkaline solution maydo this by dissolving the more soluble oxide components out of the oxideportion. Certain oxides are more soluble than others in an alkalineenvironment. For example, the oxides of manganese, vanadium, aluminum,cobalt and tin are readily soluble in an alkaline solution while others,such as those of titanium, zirconium and nickel are less soluble. Thoseoxides which are more soluble will be removed from the oxide layer tothe alkaline solution. The less soluble oxides will either remain atpart of the oxide or enter the alkaline solution as colloidal particles.Hence, the composition of the oxide portion will be altered. FIG. 1 isan STEM photomicrograph showing the effects of leaching a hydrogenstorage alloy particle with an alkaline leaching material (i.e. analkaline solution). In FIG. 1, only a portion of the hydrogen storagealloy particle has been leached.

Selectively removing the more soluble components of the oxide portion ofthe catalytic material provides for a greater concentration catalyticsites of metallic nickel and/or nickel alloy, which are resistant tooxidation and also insoluble in the alkaline solution. Nickel and nickelalloys, in their metallic state, are catalytic and electricallyconductive, and these catalytic properties are imparted to the oxideregion. The oxide region is thus more catalytic and conductive than ifit contained a higher concentration of insulating oxides.

Removing the more soluble oxide components also makes the oxide regionmore porous. An increase in porosity increases the permeability of theoxide region to the diffusion and transport of molecular hydrogen aswell as to the diffusion and transport of certain ions, such as hydrogenand hydroxyl ions. An increase in porosity also increases the surfacearea of the oxide region.

It is noted that the bulk leaching process used to create the catalyticmaterials of the present invention is distinguishable from alkaline“etching” treatments used to simply modify the initial surface oxidelayer (described above) of the hydrogen storage alloy. As discussedabove, this initial surface layer is about 1000 Angstroms thick.Alkaline etch treatments described in the '088 patent as well as the'391 application, are surface treatments used to modify the existingsurface oxide of a hydrogen storage alloy material in order to make thematerial suitable for use as the active electrode material in a metalhydride electrochemical cell (for example, a nickel metal hydride cell).When used as the active material for an electrochemical cell, thehydrogen storage alloy particles themselves may be on the order of about10 to about 70 microns in size. After the etch treatment, each hydrogenstorage alloy particle is surrounded by a relatively thin metal oxidesurface layer that may have a thickness of about 1000 Angstroms. Withinthis oxide surface layer, there are a large number of the metallicnickel and/or nickel alloy particles that are on the order of about 10to about 70 Angstroms in size. Overall, however, the fraction of thecatalytic metal particles in the thin oxide surface layer is small incomparison to the volume of metal present in the non-oxidized bulk ofthe hydrogen storage alloy particles.

In contrast, as discussed above, the leaching process used to form thecatalytic material of the present invention preferably oxidizessubstantially all of the starting hydrogen storage alloy particle.Leaching conditions (i.e., leaching time as well as temperature and pHof the leaching material) are selected which completely treat thestarting hydrogen absorbing alloy particles so that only oxides withsuspended catalytic particles remain (i.e, a “catalytic oxide”). Theleaching conditions used to make the catalytic materials of the presentinvention may be different from those used to activate the hydrogenstorage alloy materials for battery applications (i.e., since at least asignificant portion of the bulk will be leached, one or more of theleaching conditions may be more aggressive). Also, the selection of thestarting hydrogen storage alloy itself may also be different for theinstant invention than the starting material used to form an activeelectrode material for battery applications. For example, the chosenhydrogen storage alloy for the instant invention may use a higherfraction of readily dissolved elements such as V, Co, Al, and Sn.

Specifically, to form the catalytic materials of the present invention,the leaching material may be an alkaline material and the leachingconditions may be chosen so that the temperature of the alkalinematerial is preferably above about 60° C., and more preferably aboveabout 100° C. The percentage weight of the alkali metal hydroxide ispreferably at least about 30 weight %, more preferably at least about 40weight %, and most preferably at least about 60 weight %. Of course, theleaching conditions are not limited to the above ranges and may bevaried to achieve the desired results.

In another embodiment of the method of making the catalytic materials ofthe present invention, the leaching material used may be an acidicsolution. The use of an acidic solution is also within the spirit andscope of this invention. The acidic solution may be an aqueous solutionof one or more acids. Examples of acids which may be used include HF,HCl, H₂SO4, and HNO₃. Blends of two or more acids may also be used. Anexample of a blend which may be used is an aqua regia. An example of anaqua regia is a mixture of nitric acid and hydrochloric acid. Theleaching process may be implemented by “contacting” the alloy materialwith an acid (such as HF) for a predetermined period of time, at aspecific temperature and at a specific pH.

It is also possible that the desired catalytic materials be made byusing two or more leaching processes. For example, a first alkalineleaching treatment may be performed at a first set of leachingconditions (i.e., a first alkaline material as well as a first time,temperature and alkaline concentration), and then a second alkalineleaching treatment may be performed at a second set of etch conditions(i.e., a second alkaline material as well as a second time, temperatureand alkaline concentration). This process may be repeated with further,subsequently applied, alkaline leaching treatment. Alternately, one ormore of the alkaline leaching treatment may be replaced with one or moreacidic leaching processes (wherein the leaching material is an acidicsolution). Hence, the leaching process may comprise two or more acidicetch treatments. Alternately, the leaching process may comprise one ormore alkaline leaching treatment and one or more acidic leachingtreatments. In a particular embodiment, the leaching process maycomprise alternating alkaline leaching treatments and acidic leachingtreatments. This alternating acid/base treatment is an especiallyaggressive method to more fully react the starting alloy.

As discussed above, the catalyst of the present invention may be used asthe catalytic material of a fuel cell anode. Though not wishing to bebound by theory, it is possible that this fuel cell anode function ofthe instant catalysts may be assisted by deliberately leaving a portionof the starting hydrogen storage alloy it its metallic (unoxidized)state. Specifically, the dissociation of the H₂ gas reactant andsubsequent reaction with hydroxyl ions from the electrolyte to formwater with the release of an electron according to the reactionequation:

$\begin{matrix}\left. {{H_{2}(g)} + {2{OH}^{-}}}\rightarrow{{2H_{2}\; O} + {2e^{-}}} \right. & (3)\end{matrix}$may be assisted by the following sub-mechanism:

$\begin{matrix}\left. {{H_{2}(g)} + {2M}}\rightarrow{2{MH}} \right. & \left( {3a} \right) \\\left. {{2{MH}} + {2{OH}^{-}}}\rightarrow{{2M} + {2H_{2}O} + {2e^{-}}} \right. & \left( {3b} \right)\end{matrix}$where the molecular hydrogen H₂ is first absorbed by the hydrogenstorage alloy (step 3 a) and then reacted with the hydroxyl ions OH⁻from the electrolyte (step 3 b). Optimized ratios of unoxidized metalalloy material to catalytic oxide can be determined by optimizationexperiments. It is possible to produce a catalytic material having suchoptimized ratios by the appropriate choice of the starting hydrogenstorage alloy as well as the appropriate choice of conditions in thebulk leaching process used to treat the alloy.

Hence, by appropriately selecting the appropriate leaching conditionsand/or the appropriate starting material, the leaching process may alsobe used to chemically convert a desired percentage of each of thehydrogen storage alloy particles to the catalytic oxide. Specifically,in another embodiment of the invention, it is preferable that theleaching process chemically converts at least about 10% of each of thealloy particles to the catalytic oxide. It is more preferable that theleaching process chemically converts at least about 25% of each of thealloy particles to the catalytic oxide. It is most preferable that theleaching process chemically converts at least about 50% of each of thealloy particles to the catalytic oxide. In another embodiment, theleaching conditions and/or the starting materials may be chosen so thatthe leaching process chemically converts at least about 75% of each ofthe alloy particles to the catalytic oxide. Preferably, the leachingprocess converts at least about 90% of each of the alloy particles tothe catalytic oxide.

It is also possible that the fuel cell function of the instant catalystbe promoted by forming a catalyst which is “compositionally graded”. Asused herein, compositional grading refers to forming the catalyst sothat there is a continuous change (linear or non-linear) in some aspectof the composition in a chosen direction. (Preferably, there is acontinuous increase or decrease in some aspect of the composition). Forexample, referring to FIG. 4, the catalyst incorporated into the anode14 may be compositionally graded so that there is an increase ordecrease in the density of the catalytic sites from the hydrogen inputside (i.e., adjacent the hydrogen compartment 13) to the electrolyteside (i.e., adjacent the electrolyte 12). In one embodiment, thecatalyst is compositionally graded so that there is a continuousdecrease in the density of the catalytic sites from the hydrogen inputside (i.e., adjacent the hydrogen compartment 13) to the electrolyteside (i.e., adjacent the electrolyte 12) of the anode 14.

As discussed above, it is also possible to form a support whichcomprises materials other than oxides. For example, the support may alsocomprise chlorides, phosphides, silicides, and carbides. These materialsmay also be made using a deep, penetrating leaching process. Theleaching material is appropriately chosen to convert the startinghydrogen storage alloy material to the desired support material. (Ofcourse mixtures of materials may also be formed—with or without oxides).For example, a catalytic phosphide may be formed comprising a finelydivided metal particulate embedded in a phosphide.

In an alternate embodiment of the invention, by selecting theappropriate starting material as well as an appropriate leaching processit is also possible extract (i.e., dissolve out) substantially all ofthe soluble oxide components of the starting material, leaving behindonly the small, catalytically active particles. These catalyticallyactive particles may be affixed to a support material or a supportstructure. For example, they may be mixed with a carbon supportmaterial. Alternately, they may be affixed to a support structure suchas a conductive grid. Also, they be even be mixed together with abinder, such as PTFE, for mechanical stability.

In the embodiments of the leaching processes described above, theleaching process involved a chemical treatment of the hydrogen storagealloy powder. This may be referred to as “chemical leaching”. In analternate embodiment of the leaching process, the leaching treatment maybe electrochemically assisted. That is, a potential may be applied tothe hydrogen storage alloy powder so as to make it easier to convert theoxidizable components of the alloy to their respective oxides or toremove the more soluble oxides from the material after the oxides areformed. This type of electrochemically assisted leaching is referred toherein as “electrochemical leaching”. The electrochemical leaching issimilar in concept to electrochemically assisted etching (applyingpotential to assist the etching process) which is described in detail inthe '088 patent.

From the discussion above, it is seen that by first formulating ahydrogen absorbing alloy material with an appropriate composition andthen subjecting this alloy to a leaching process having the appropriateleaching conditions conditions (i.e., time of leaching as well astemperature and pH of the leaching material), substantially the entirestarting alloy may be oxidized to form a highly catalytic materialcomprising a nickel and/or nickel alloy particulate embedded in an oxidesupport. Generally, by carefully choosing the starting alloy as well asthe leaching conditions, this catalytic material may be designed to havethe desired catalytic, electrochemical, and physical properties. As seenfrom the above discussion many different properties may be modified.These properties include, but are not limited to 1) the size, density,roughness and composition of the catalytically active sites, 2) thecomposition of the oxide support material, 3) crystal structure of thecatalytic sites, 4) composition of the oxide support, 5) the grain sizeof the oxide support, 6) the surface area and porosity of the oxide, 7)the permeability of the oxide to hydrogen gas and to ionic transport(including, but not limited to, hydrogen and hydroxyl ion transport),and 8) the percentage of the hydrogen storage alloy particle convertedto oxides.

Furthermore, it is seen from the above discussion, that the catalyticmaterial of the present invention may be formed to make it particularlywell suited for use as the catalytically active material for hydrogenconsumption in a fuel cell anode. Specifically, the catalytic materialmay be formed so that it is 1) highly catalytic for the consumption ofmolecular hydrogen, 2) electrically conductive for the transport ofelectrons, 3) permeable to the diffusion and transport of hydrogen gas,4) permeable to the diffusion and transport of ions such as hydrogenions and hydroxyl ions, 5) permeable to the diffusion of a liquidelectrolyte, and 6) a barrier to the gas phase H₂ on one side of theanode and the electrolyte on the other side. All of the aforementionedproperties are desirable properties for using the catalytic material ofthe present invention as the active material for a fuel cell anode.

It is noted that the catalytic materials of the present invention mayalso include disordered catalytic materials. Examples of disorderedmaterials are provided in U.S. Pat. No. 4,487,818, the contents of whichare incorporated by reference.

Generally, the catalytic material of the present invention may be usedas the active material for the anode of any fuel cell. Examples of fuelcells include proton exchange membrane fuel cells (PEM), alkaline fuelcells (AFC), phosphoric acid fuel cells (PAFC), molten carbonate fuelcells (MCFC), and solid oxide fuel cells (SOFC). In all cases, while theelectrolyte and sub-reactions can be different, the basic point of H₂gas dissociation to form water with release of current, in a hostileenvironment is common.

In one embodiment, the catalytic material may be used as the activematerial for the anode of an alkaline fuel cell. As shown in FIG. 5, analkaline fuel cell 20 comprises an anode 24, a cathode 26 and analkaline electrolyte 22 held within a porous non-conducting matrixbetween the anode 24 and the cathode 26. Potassium hydroxide istypically used as the alkaline electrolyte in an alkaline fuel cell. Theanode 24 comprises a conductive substrate 24A and an anode layer 24Blayer supported on the substrate 24A. The cathode 26 comprises aconductive substrate 26A and a cathode layer 26B support on thesubstrate 26A.

A hydrogen gas is fed to the anode 24 and an oxygen gas is fed to thecathode 26. In the embodiment shown, the hydrogen gas is fed to theanode 24 via the hydrogen compartment 13, and the oxygen gas is fed tothe cathode 26 via the oxygen/air compartment 17. The reactant gasesdiffuse through the electrodes to react with the electrolyte 22 in thepresence of the catalyst to produce water, heat and electricity. At theanode 24 the hydrogen is electrochemically oxidized and give upelectrons according to the reaction:H₂(g)+2OH⁻→2H₂O+2e ⁻  (4)The electrons so generated are conducted from the anode 24 through anexternal circuit to the cathode 26. At the cathode 26 electrons areelectrochemically combined with the oxidant according to the reaction:½O₂(g)+H₂O+2e ⁻→2OH⁻  (5)A flow of hydroxyl (OH⁻) ions through the electrolyte 22 completes theelectrical circuit.

As discussed, the anode 24 comprises an anode layer 24B affixed to aconductive substrate 24A. FIG. 6 shows a detailed example of anembodiment of the anode layer 24B. Referring to FIG. 6, the anode layer24B includes the instant catalytically active material 32 and apolymeric hydrophobic material 34. An example of a polymeric hydrophobicmaterial is PTFE. The active material 32 may be intermixed with thehydrophobic material 34. The catalytically active material 32 forms anetwork of electrolyte-filled channels through the anode layer 24B. Theabove described electrochemical reactions occur at the surface of thecatalytically active particles. The porous hydrophobic material 34 bindsthe anode layer 24B together and provides a network of channels throughwhich reactant gases gain access to the catalytic surface of the activematerial 32. In an alternate embodiment, the hydrophobic material may bein the form of a hydrophobic layer (rather than being intermixed withthe catalytic material). The hydrophobic layer may be placed adjacent toa catalyst layer. The catalyst layer may be in the form of catalyticmaterial which is affixed to a conductive substrate.

In another embodiment, the catalytically active material of the presentinvention may be used as the active material for the anode of a protonexchange member (PEM) fuel cell. A PEM fuel cell is described in detailin U.S. Pat. No. 5,234,777, the disclosure of which is incorporatedherein by reference. A PEM fuel cell uses a proton exchange membrane(also known as a solid polymer electrolyte) to provide ion exchangebetween the cathode and anode electrodes. The anode and cathodeelectrochemical reactions for a proton exchange membrane (PEM) fuel cellare as follows:

$\begin{matrix}\left. {H_{2}(g)}\rightarrow{{2H^{+}} + {2e} -} \right. & (6) \\\left. {{\left( {1/2} \right){O_{2}(g)}} + {2H^{+}} + {2e^{-}}}\rightarrow{H_{2}O} \right. & (7)\end{matrix}$Like the anode reaction of the alkaline fuel, the alkaline reaction fora PEM fuel cell also involves the oxidation of the hydrogen gas fuel.For the PEM fuel cell, the electrical circuit of the fuel cell iscompleted by positive ion movement in the form of a hydrogen atom fromthe anode to the cathode (in contrast to the alkaline fuel cell wherethere is negative ion movement in the form of a hydroxyl ion fromcathode to anode.

Like the anode of the alkaline fuel cell, the anode of the PEM fuel cellalso comprises an anode layer affixed to a conductive substrate.However, in the case of the PEM fuel cell, a hydrophobic material is notneeded; hence, the anode layer may simply consist of the instantcatalytically active material.

Relative comparisons of the efficiency of the present invention supercatalysts versus that of platinum and palladium have not yet been done.It fact, it is still within the spirit and scope of the invention thateven if worse than platinum and/or palladium, they may still be better.This is not only because these nickel catalysts are so much lessexpensive on a relative basis than either platinum or palladium, butalso because the size and surface area can be made much smaller/higherrespectively. The overall consequence is that the catalyst user has ahigher available concentration per unit area of the catalyst availablecompared to either platinum or palladium. Further, the long termbenefits other than cost may be the ability of these “ultra finecatalysts” to operate effectively in unusually hostile (i.e., poisoning)environments without degradation.

EXAMPLE 1

In this example, a nickel metal hydride (NiMH) rechargeable battery ischosen as the test bed to demonstrate the capability of hydrogen gasabsorption of the current invention in a hostile gas environment. Rawmaterials with purity higher than 99% were mixed and loaded in a vacuuminduction furnace, melted, and poured into a steel mold. The ingot waspulverized into a 200-mesh powder and compacted onto a metal substrateto form an electrode belt. The electrode was used as the negativeelectrode in conjunction with nickel hydroxide positive electrodes,separators, and a 30% KOH electrolyte to fabricate typical sealed NiMHrechargeable batteries.

The hydrogen storage alloy was activated under a heat treatment of 60°C. for five days. The surface of the activated alloy comprises a metalparticulate embedded in a porous metal oxide. The oxide prevents furtheroxidation of the alloy and the porosity in the oxide make it possiblefor both gas and electrolyte to penetrate. The metal particulate,consisting essentially of substantially pure metallic nickel and/or anickel alloy, contributes to the catalytic nature of the surface.

The battery was charged under C/10 rate for 20 hours. The cell voltageand the cell pressure were monitored during the entire charge process(FIG. 7). It is clear from FIG. 7 that when the cell was charged closeto its full capacity, the cell voltage started to increase from the 1.4volt plateau to the 1.5 voltage overcharge plateau. The cell pressurealso increased from 0 PSI to 100 PSI. A small sample of gas waswithdrawn from the cell and the gas contents was determined by gaschromatograghy (GC) to be 96% H₂, 1% O₂, 2.5% N₂, and 0.5% CH₄. Thereare two possible mechanisms for this hydrogen domination phenomenon. Thefirst one is the local heating of the hydrogen storage alloy due to thehydrogen-oxygen recombination and dehydride part of the charged negativeelectrode. The second possible mechanism is the lowering in the hydrogengas evolution potential in the negative electrode due to the presence ofoxygen evolved from the positive electrode during overcharge.

After the cell was charged to 200% of its rated capacity, it was leftidle in the open-circuit configuration for five hours. The cell voltageand cell pressure were monitored again during this resting period (FIG.8). The cell pressure went down from 100 PSI to less than 40 PSI inabout five hours due to the hydrogen gas absorption into the negativeelectrode demonstrating that the activated surface of the hydrogenstorage alloy acts as a catalyst effective to facilitate thedecomposition of molecular hydrogen into atomic hydrogen. The atomichydrogen is absorbed into the bulk of the hydrogen storage alloy eitherunder presence of hostile gas species, such as oxygen and othercarbon-containing gas.

EXAMPLE 2

An identical NiMH battery as used in Example 1 was charged anddischarged 500 times. The heavily cycled battery was then charged underC/10 rate for 20 hours. The cell voltage and pressure were monitoredduring the entire charge process (FIG. 9). As shown in FIG. 9, the cellpressure increased from 0 PSI to 150 PSI. A small sample of gas waswithdrawn from the cell and the gas content determined by gaschromatography (GC) was 96.3% H₂, 0.4% O₂, and 3.3% N₂. After the cellwas charged to 200% of its rated capacity, it was left idle in theopen-circuit configuration for five hours. The cell voltage and pressurewere monitored during this open circuit period (FIG. 10). The cellpressure decreased from 150 PSI to less than 80 PSI in about five hoursdemonstrating that, even after 315 cycles, the alloy surface was stillable to act as a catalyst effective to decompose hydrogen gas intoatomic hydrogen which could then be absorbed into the bulk of thehydrogen storage alloy material.

It is to be understood that the disclosure set forth herein is presentedin the form of detailed embodiments described for the purpose of makinga full and complete disclosure of the present invention, and that suchdetails are not to be interpreted as limiting the true scope of thisinvention as set forth and defined in the appended claims.

1. A method for making a catalyst, comprising the steps of: providingalloy particles; and leaching at least 10,000 Angstroms of said alloyparticles.
 2. The method of claim 1, wherein said leaching step leachesat least 25% of the volume said alloy particles.
 3. The method of claim1, wherein said leaching step leaches at least 50% of the volume saidalloy particles.
 4. The method of claim 1, wherein said leaching stepleaches a predominate portion of said alloy particles.
 5. The method ofclaim 1, wherein said leaching step comprises the step of leachingsubstantially all of said alloy particles.
 6. The method of claim 1,wherein said leaching step comprises the step of converting said alloyto at least one material selected from the group consisting of oxides,phosphides, chlorides, suicides, carbides, sulfides, and mixturesthereof.
 7. The method of claim 1, wherein said leaching step comprisesthe step of oxidizing said alloy particles.
 8. The method of claim 1,wherein said leaching step comprises the step of: contacting said alloyparticles with an alkaline material.
 9. The method of claim 8, whereinsaid alkaline material comprises an alkali metal hydroxide.
 10. Themethod of claim 9, wherein said alkali metal hydroxide is selected fromthe group consisting of potassium hydroxide, sodium hydroxide, lithiumhydroxide, and mixtures thereof.
 11. The method of claim 1, wherein saidleaching step comprises the step of: contacting said alloy particleswith an acidic material.
 12. The method of claim 1, wherein saidleaching step comprises the steps of: contacting said alloy particleswith an alkaline material; and contacting said alloy particles with anacidic material.
 13. The method of claim 12, wherein said acidicmaterial comprises an acid selected from the group consisting of HF,HCl, HNO₃, H₂SO₄, and mixtures thereof.
 14. The method of claim 1,wherein said leaching step comprises the step of: alternatinglycontacting said alloy particles with alkaline and acidic materials. 15.The method of claim 1, wherein said leaching step is chemical leaching.16. The method of claim 1, wherein said leaching step is electrochemicalleaching.
 17. The method of claim 1, wherein said alloy particles arehydrogen storage alloy particles.
 18. The method of claim 1, whereinsaid catalyst is a catalyst powder comprising a nickel or nickel alloyparticulate having an average particle size of between about 10Angstroms and about 70 Angstroms dispersed in a support matrix, saidpower formed predominantly of its nickel or nickel alloy particulate andsupport matrix.
 19. The method of claim 1, wherein said leaching stepleaches less than the entire volume of said alloy particles.